Urea aldehyde molding compositions containing a latent curing catalyst



Patented Oct. Id 193 8 2,133,689

UNITED STATES PATENT OFFICE aiaassa UREA ALDEHYDE MOLDING GOMPOSITIGNS ggSNi IAINING A LATENT CURING CATA- Carieton Ellis; Montclair, N. 1., minor, .by means cuts, to Piaskon Company Incorporated. New York, N. Y.. a corporation oi Delaware No Drawinr. Application April 30, 1987, Serial No. 139,9

9Claims.(CL106-22) This invention relates to urea aldehyde moldbecause of the possibility of toxic substances s compositions containing a curing catalyst of being introduced.

the latent type. and to the process of making and According to H. M. Dawson and M. B. Dyson using the same. (J. C. S., 1933, 49 and 1133) and. other investi- By a latent catalyst I mean a substance of gators, such salts decompose to give the metallic 5 811011 y e as defined in my U. 8. Patent 1,905,999, halogenate and the corresponding hydroiiy carthat is,,one which is active only when a given boxylic 361d.' It is probable that the curins temperature is reached. such a curing agent I action oi such substances is due to the free acid should preferably release an acid only at a temliberated, but partial hydrolysis of the metallic 1o perature near that at which hot pressing is ordisalt lay-product or the reaction may aid the catal- 1o narily carried out, namely in the neighborhood ysis. In the case of iii-halogenated acids, the of 150 C, A latent catalyst is important in that reaction .may take a diiierent course. The above it allows a composition to be prepared which may theory 18 'fl n explanation only. and I do be stored for long periods before use and when not wish to be limited thereby; I h v deterthe composition is placed in a hot die and submined. however, that if crystalline sodium mono- 15 jected to pressure, the cure" of the composition, hlorace ate is hea ed t a p rfl m Biwh 88 i. e. polymerization .and condensation thereof, is sed in 111 8. in Mid mummified which 8" facilitated by the acid released by said catalyst. a positive test with wet'litmus paper but gives a Other prerequisites of such a catalyst are: (i) it negative test with silver nitrate, thus proving 20 should be stable over a long period of time and that an acid is liberated which is not hydrogen 20 at temperatures below the temperature oi-hot chloride. D g: (2) it should be substantially neutral In making ur resln m l i g 1111 before being broken down by the heat and pres- I may react 1 mole oi urea or equivalent subsure of molding; (3-) it should be colorless, and stance with 1 to 2 moles, preferably-1.5 moles, of

Yield colorless products on decomposing: and (4) formaldehyde or equivalent substance under al- 25 it should not give oil! an acid so strong or so rekalinc.- neut a or cid io and Obtain active that it might react with the steel oi the thereby a hv rop or ev n wat r-s l ble. die and thus bring about corrosionl It is the densation product. This may be incorporated Purpose and object or the prevent invention to with a cellulosic material such as. fo pl provide molding compositions with a compound paper'pulp. alpha c u w od flou a d the so of this character which will operate to materially like. In so doing, the ur a-f m y resin facilitate-the hot pressing of urea-aldehyde omreacts with the cellulose to produce what is positions in the formation of light-colored shaped own as Elllcwure i p l is necesarticles of ample water, shock and heat resistsary to remo from the ix ure t s v nce. usually water, in which the urea-formaldehyde 5 I have discovered that the prerequisites of a condensation was accomplished. This can be latent catalyst are possessed by the salts of the done by drying, either at atmospheric or reduced monoand dl-halogenated aliphatic carboxylic pressure, at atemperature desirably below 00 C. acids and by the salts of halogenated acetic acid The dried material is usually finely mum! and 40 and alpha and alpha-beta halogenated 1 screened. It is customary to include a curing 4o es of acetic acid in particular. Rather pei y mg i zafifi h as z n stesrste- "marl? the twins p pe y possessed by the a monoand (ii-halogen compounds is not evinced A convenient way to incorporate the catalyst is simply to dissolve the salt in the resin syrup by the m'halogen As bef the latter'is mixed with the drier Wet- 4s amples of such compounds may-be menubned ti ents such as ethyl alcohol or acetone may salts such as chloracetates bromacetates iodoa t t be added if desired. Another way is to thorce a es. iiucracetates, dichloracetates, a-chlorougmy grind the dried glucamue mixture with pmpmmm- *dlchmrpmpmmflf 'P' the dry salt. I: this method is used. the catalyst pmplmates' 'pdlcmrsteames and the should be groundin before the lubricant is added. so

I The salts may be of any base metal 91110118 for after such a substance as zinc stearate is .those preferred may be mentioned sodi m, 10- added grinding is practically impossible tassium, ammonium, aluminum, zinc, calcium, Having a molding compound containing reacmagnesium, and so forth; Such metals as lead tive urea-formaldehyde resin (combined it deand mercury are applicable but are not desirable sired as a glucanure compound with the filler). l5

a latent curing catalyst as provided in this invention, and a lubricant, the composition may be subjected to hot pressing usually eflected at a temperature of about 125 to 150 C. under a pressure of from about 2000 to 3500 pounds per square inch, to mold any desired article. The salts of the halogenated acids liberate an acid substance under molding conditions, and eiiectively harden the resin. It should be noted that the catalysts claimed do not liberate dangerous hydro-halogen acids, but merely the comparatively innocuous carboxylic acid which is suiiicient, however, to bring about a cure. This is important because repeated use of molding compositions containing curing catalysts which depend on the liberation of, say, hydrogen chloride or bromide, as the active principle tends to cause pitting, staining and corrosion of molds, thus deteriorating an expensive piece of apparatus. Furthermore, these catalyzing salts are comparatively cheap, easy to prepare, substantially stable at ordinary temperatures, are light colored themselves and yield light-colored products, have relatively low molecular weights, and are hence efllcient and economical.

In presenting the following examples illustrative of the invention, I do not wish to be limited by their procedures or proportions, as modifications within the scope of the invention will present themselves to one skilled in the art.

Example 1.1120 parts by weight of a 37% formaldehyde solution and 552 parts by weight urea were boiled under reflux at pH '7 for 1 hours. f the resulting syrup, 200 parts were mixed with 62 parts of alpha flock and the composition was dried at 64 C. in acurrent of air, and ground. This material was hot-pressed at 140 C., for minutes, without, adding any activator. It would not cure, the moldings being soft and sticky, of wan heterogeneous appearance, and possessing low mechanical strength.

100 parts of the powder and 1 part of the sodium salt of monochloracetic acid were ground together in a ball mill and subsequently further ground with 0.35 part of zinc stearate.

The activated composition was molded at 140 C., 3500 pounds per square inch, for 5 minutes.

-The material was soft flowing, the moldings being well formed and glazed, white strong, and translucent. An object was immersed in boiling water for 15 minutes and it was substantially unafiected, the glaze remaining excellent.

A portion of the composition was stored in a closed container for 7 months, and then molded as before. Again the flow was soft and molded objects were obtained which were .well cured. The powder did not deteriorate in storage.

Example 2.A blank molding composition was prepared as described in the first paragraph of Example 1. This was activated with 1 per cent sodium dichioracetate by grinding the components together in a, ball mill. Zinc stearate was also added to the extent of 0.25 per cent.

The finished composition was molded at 140 0., 3500 pounds per square inch, for 5 minutes.

vThe molded objects were well formed and glazed,

light colored and translucent.

Example 3.-l50 parts of 37% formaldehyde solution and '75 parts of urea were boiled together under reflux at pH 7 for 1 hour. 1.5 parts of neutral sodium-monochloracetate were added to the syrup and the whole mixed with 60 parts of alpha flock. The mixture was dried in a current of air at 60 C. and subsequently ground to a powder.

The product was molded at 140 0., 3500 pounds per square inch, for 5 minutes. The moldings obtained were well cured, possessed a high glaze, were light colored and translucent.

Example 4.-A blank molding composition was prepared as follows: 1000 parts of neutral 37% aqueous formaldehyde and 500 parts of urea were boiled under reflux for 1 hour. The resulting syrup was mixed with 400 parts of alpha flock, dried at 64 C. and ground.

The powder was activated with 1 per cent zinc monochloracetate by grinding the powder and dry salt in a ball mill; 0.25 per cent zinc stearate was also ground in. The product was molded at 140 C., 3500 pounds per square inch, for 5 minutes.

The molded objects were quite translucent,

light colored, well formed and glazed. The flow of the composition was soft. A molding, immersed in boiling water for 15 minutes, absorbed 4.5 per cent moisture, which is average for a urea-formaldehye molding composition.

Example 5.--Uslng a blank molding composition prepared as described in the first paragraph of Example 4, it was activated by grinding in a ball mill with l per cent of ammonium mono- -chloracetate. The moldings made at 140 C.,

3500 pounds per square inch, for 5 minutes, were substantially of the same appearance as those of Example 4, the composition curing satisfactorily.

Example 6.-Example 5 was repeated using 1 per cent of calium monochloracetate. Excellent, well cured, translucent, light-colored objects were formed on molding. After being immersed in,

boiling water for 15 minutes, the moldings absorbed an average of 2.1 per cent water.

Example 7.--Example 5 was repeated using 1 per cent sodium -chloropropionate. The flow of the finished composition was soft. The molded articles were well formed, cured, and glazed, light colored, and translucent. when immersed in boiling water for 15 minutes the molded pieces absorbed 3 per cent water.

Example 8.Example 5 was repeated using 1 per cent ammonium a-chloropropionate as the activator. The appearance of the molded products was the same as of those produced according to Example 7.

Example 9.Sodium iodoacetate was tested following the procedure of Example 5. The moldings were light colored, very translucent, well formed and glazed, strong and apparently well cured. The flow of the composition was soft.

Example 10.Example 9 was repeated, using sodium bromo-acetate. The moldings obtained were well cured, and resembled those of Example 9 in appearance. when immersed-in boiling water for 15 minutes, the glaze was scarcely affected and the water absorption was 7.4 per cent.

What I claim is:

1. A urea-formaldehyde molding composition containing a latent catalyst comprising a salt of chloracetic acid.

2. A urea-formaldehyde molding composition containing a latent catalyst comprising a salt of chlorpropionic acid.

3. A urea-formaldehyde molding composition containing a latent catalyst comprising a salt of a halogenated aliphatic carbomlic acid selected from the class consisting of the monoand dihalogenated straight chain mono-carboxylic acids which remains substantially neutral before being broken down by heat and pressure during molding and which, upon being broken down, liberates an hyde molding composition, the step of adding to a mixture comprising cellulose and urea-formaldehyde resin. a latent catalyst comprising a salt or a halogenated aliphatic carboxylic acid selected from the class consisting 'of the monoand di-halogenated straight chain mono-carboxylic acids which remains substantially neutral beiore being broken down by heat and pressure during molding and which, upon being broken down. liberates an acid not corrosive to the metal structure of molds.

'l. a molding composition comprising a sincanure and a small proportion of a salt of chloracetic acid.

8. A molding composition comprising a glumore and a small proportion of a salt of a chlorinated straight chain mono-carboxylic acid selected from the class consisting of the monoand di-halogenated straight chain mono-carboxylie acids which remains substantially neutral bei'ore being broken down by heat and pressure during molding and which is reactive at molding temperature to release a curing proportion 01 an acid not corrosive to the metal structure of molds.

9. A molding composition comprising a glucanure and a small proportion of a salt of a halogenated aliphatic carboxylic acid selected from the class consisting of the monoand dihalogenated straight chain mono-carboxylic acids which remains substantially neutral before being broken down by heat and pressure during molding and which is reactive at molding temperature to release a curing proportion of an acid not corrosive to the metal structure oi molds.

CARLETON ELLIS.

DISCLAIMER 2,133,689.0arleton Ellis, Montclair, N. .i.

CONTAINING a LATENT Cosmo Unna Camus-r. Patent dated October 18, 1938.

Amman Momma Comosrnons Disclaimer filed July 22, 1941, by the assignee,Plaskoa 0ompwny, 1morpoall moldin compositions comprising a glucanure of a chlorinated stra' ht chain monocarbo chloracetic acid; and

rising a glucanure and a small xylic acid in which sai further disclaims from claim 9 all molding cczgipos tions comproportion of a salt of a halogens ah xylic acid in which said salt is a salt of chloracetic acid.

7 of said patent; and further disclaims from claim compositions containin a latent catalyst in wlnch loracetic acid; and furtfi er disclaims from claim 8 ortion of a salt andasmallpro saltisasaltof phatic carhyde molding composition, the step of adding to a mixture comprising cellulose and urea-formaldehyde resin. a latent catalyst comprising a salt or a halogenated aliphatic carboxylic acid selected from the class consisting 'of the monoand di-halogenated straight chain mono-carboxylic acids which remains substantially neutral beiore being broken down by heat and pressure during molding and which, upon being broken down. liberates an acid not corrosive to the metal structure of molds.

'l. a molding composition comprising a sincanure and a small proportion of a salt of chloracetic acid.

8. A molding composition comprising a glumore and a small proportion of a salt of a chlorinated straight chain mono-carboxylic acid selected from the class consisting of the monoand di-halogenated straight chain mono-carboxylie acids which remains substantially neutral bei'ore being broken down by heat and pressure during molding and which is reactive at molding temperature to release a curing proportion 01 an acid not corrosive to the metal structure of molds.

9. A molding composition comprising a glucanure and a small proportion of a salt of a halogenated aliphatic carboxylic acid selected from the class consisting of the monoand dihalogenated straight chain mono-carboxylic acids which remains substantially neutral before being broken down by heat and pressure during molding and which is reactive at molding temperature to release a curing proportion of an acid not corrosive to the metal structure oi molds.

CARLETON ELLIS.

DISCLAIMER 2,133,689.0arleton Ellis, Montclair, N. .i.

CONTAINING a LATENT Cosmo Unna Camus-r. Patent dated October 18, 1938.

Amman Momma Comosrnons Disclaimer filed July 22, 1941, by the assignee,Plaskoa 0ompwny, 1morpoall moldin compositions comprising a glucanure of a chlorinated stra' ht chain monocarbo chloracetic acid; and

rising a glucanure and a small xylic acid in which sai further disclaims from claim 9 all molding cczgipos tions comproportion of a salt of a halogens ah xylic acid in which said salt is a salt of chloracetic acid.

7 of said patent; and further disclaims from claim compositions containin a latent catalyst in wlnch loracetic acid; and furtfi er disclaims from claim 8 ortion of a salt andasmallpro saltisasaltof phatic car- 

